Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 3, 2025
This
study
presents
a
copper-catalyzed,
substrate-controlled
regio-
and
enantioselective
intermolecular
hydrosilylation
method
capable
of
accommodating
broad
scope
alkenes
prochiral
silanes.
The
approach
offers
an
efficient
versatile
pathway
to
generate
enantioenriched
linear
branched
alkyl-substituted
Si-stereogenic
Key
features
this
reaction
include
mild
conditions,
simple
catalytic
systems,
compatibility
with
diverse
substrates,
high
yields
enantioselectivities.
While
methods
create
chiral
carbon
centers
stereochemically
defined
silicon
have
been
developed,
the
ability
both
simultaneously
would
be
value.
Here
authors
present
substratecontrolled
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(32), P. 6054 - 6059
Published: Aug. 10, 2022
A
novel
strategy
of
copper-catalyzed
regio-
and
enantioselective
hydrosilylation
4-substituted
vinylidenecyclohexanes
with
silanes
was
developed.
In
this
protocol,
various
allenes
were
used
to
afford
the
corresponding
(cyclohexylidene)ethyl
in
moderate
high
yields
good
enantioselectivities.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(10), P. 4530 - 4540
Published: March 4, 2022
A
cobalt-catalyzed
intermolecular
three-component
coupling
of
arenes,
ethylene,
and
alkynes
was
developed
using
the
well-defined
air-stable
cationic
bis(phosphine)
cobalt(I)
complex,
[(dcype)Co(η6-C7H8)][BArF4]
(dcype
=
1,2-bis(dicyclohexylphosphino)ethane;
BArF4
B[(3,5-(CF3)2)C6H3]4),
as
precatalyst.
All
three
components
were
required
for
turnover
formation
ortho-homoallylated
arene
products.
range
directing
groups
including
amide,
ketone,
2-pyridyl
substituents
on
promoted
reaction.
The
method
exhibited
broad
functional
group
tolerance
allowing
late-stage
functionalization
two
drug
molecules,
fenofibrate
haloperidol.
series
control
reactions,
deuterium
labeling
studies,
resting
state
analysis,
well
synthesis
substrate-
product-bound
η6-arene
complexes
supported
a
pathway
involving
C(sp2)–H
activation
from
cobalt(III)
metallacycle.
Catalysis Science & Technology,
Journal Year:
2022,
Volume and Issue:
12(13), P. 4380 - 4387
Published: Jan. 1, 2022
In
the
present
study,
mechanism
of
a
cobalt-catalyzed
hydroarylation
reaction
between
N
-pyridylindole
and
1,6-enynes
origin
its
stereoselectivity
have
been
systematically
investigated
using
DFT
calculation
method.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(43)
Published: Sept. 8, 2023
Abstract
Palladium‐catalyzed
asymmetric
hydrofunctionalization
of
alkenes
is
one
the
most
powerful
and
straightforward
methods
to
forge
a
new
C−H
bond
C−X
(X=C,
N,
O,
F,
Si
etc)
bond,
which
provides
an
efficient
way
obtain
valuable
enantioenriched
molecules
from
cheap
readily
available
feedstocks.
Catalytic
simple
challenging
but
still
highly
sought
after.
This
review
will
mainly
focus
on
recent
advances
in
Palladium
catalyzed
over
past
decade,
including
hydroamination,
hydrooxygenation,
hydrofluorination,
hydrosilylation,
hydroarylation,
hydroalkenylation
hydrocarbonylation.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(21), P. 4526 - 4531
Published: May 18, 2024
We
report
a
novel
organic
photoredox
catalysis
to
achieve
unprecedented
γ-(hetero)aryl/alkenyl-δ-silyl
aliphatic
amines
via
silyl-mediated
distal
(hetero)aryl/alkenyl
migration
of
aromatic/alkenyl
bearing
unactivated
alkenes
with
hydrosilanes.
This
protocol
features
mild
and
metal-free
reaction
conditions,
high
atom
economy,
excellent
selectivity,
functional
group
compatibility.
Mechanistic
studies
suggest
that
silylation
(hetero)aryl/alkenylation
involve
hydrogen
transfer
subsequent
1,4-migration
remote
from
nitrogen
carbon.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3369 - 3375
Published: Feb. 16, 2024
Substituted
cyclic
alcohol
is
one
of
the
pharmaceutically
essential
scaffolds.
Here,
we
report
photoredox/cobalt-catalyzed
reductive
cyclization
alkynals
using
H2O
for
catalyst
turnover.
This
method
was
applied
to
aliphatic
and
aromatic
aldehydes
five-,
six-,
seven-membered
(heterocyclic)
ring
formation
with
various
substitutions
on
alkyne
units.
H2O-added
protocol
further
developed
into
a
one-pot
transformation
from
acetals
through
in
situ
generated
aldehydes,
which
shortened
synthetic
path
reaction.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(1)
Published: Nov. 8, 2022
Despite
the
advances
in
area
of
catalytic
alkene
hydrosilylation,
enantioselective
hydrosilylation
alkenes
bearing
a
heteroatom
substituent
is
scarce.
Here
we
report
rhodium-catalyzed
β,β-disubstituted
enamides
to
directly
afford
valuable
α-aminosilanes
highly
regio-,
diastereo-,
and
manner.
Stereodivergent
synthesis
could
be
achieved
by
regulating
substrate
geometry
ligand
configuration
generate
all
possible
stereoisomers
high
enantio-purity.
